Detergent compositions with oleoyl sarcosinate and polymeric dispersing agent

ABSTRACT

The present invention provides a deterent composition comprising: 
     (a) at least 0.1% of an oleoyl sarconsinate of the formula: ##STR1## wherein M is hydrogen or a cationic moiety; and (b) from about 0.05% to about 15% of a polymeric dispersing agent selected from the group selected from the group consisting of polycarboxylates, polyethylene glycol polymers, polyaspartates and mixtures thereof.

TECHNICAL BACKGROUND

This invention relates to detergent compositions containing detersivesurfactant and polymeric dispersing agent. In particular, this inventionrelates to detergent compositions including oleoyl sarcosinate.

BACKGROUND ART

Oleoyl sarcosinate is described in the following patents andpublications: U.S. Pat. Nos. 2,542,385; 3,402,990; 3,639,568; 4,772,424;5,186,855; European Patent Publication 505,129; British PatentPublication 1,211,545; Japanese Patent Publication 59/232194; JapanesePatent Publication 62/295997; Japanese Patent Publication 02/180811; andChemical Abstracts Service abstracts No.s 61:3244q, 70:58865x, and83:181020p.

It has been found that certain oleoyl sarcosinates can provide excellentcleaning performance and are particularly soluble in the wash solutionwhen incorporataed into a detergent composition, particularly granularcompositions. Furthermore, detergent compositions containing theseoleoyl sacrosinates in combination with one or more polymeric dispersingagents can additionally provide excellent particulate clay soil removal.The compositions also provide excellent color care for dyed fabrics andexcellent skin mildness for handwash operations. These and otheradvantages of the present invention will be seen from the disclosureshereinafter.

SUMMARY OF THE INVENTION

The present invention provides a detergent composition comprising:

(a) at least 0.1% of oleoyl sarcosinate of the formula: ##STR2## whereinM is hydrogen or a cationic moiety; and

(b) from about 0.05% to about 15% of a polymeric dispersing agentselected from the group selected from the group consisting ofpolycarboxylates, polyethylene glycol polymers, polyaspartates andmixtures thereof.

Preferred compositions further comprise at least about 0.5% of adetersive surfactant, other than said oleoyl sarcosinate surfactant,selected from anionic and nonionic detersive surfactants.

Particularly preferred compositions of the present invention alsocontain builders, i.e. zeolite and/or silicate.

This invention further provides a method for improving the performanceof detergents containing polymeric dispersing agent and detersivesurfactant by additionally incorporating into such composition at leastabout 0.1% by weight of the composition, of the oleoyl sarcosinatesurfactant described above.

DETAILED DESCRIPTION OF THE INVENTION

1. Oleoyl Sarcosinate

The present invention compositions comprise oleoyl sarcosinate, in itsacid and/or salt form selected as desired for the compositions and usesherein, having the following formula: ##STR3## wherein M is hydrogen ora cationic moiety. Preferred M are hydrogen and alkali metal salts,especially sodium and potassium. Oleoyl sarcosinate is commerciallyavailable, for example as Hamposyl O supplied by W. R. Grace & Co.Compositions o according to the present invention typically comprises atleast 0.1%, preferably from about 0.5% to about 80%, preferably fromabout 1% to about 40%, and most preferably from about 2% to about 30%,of oleoyl sarcosinate by weight of the composition.

In addition to the commercially-available oleoyl sarcosinate, oleoylsarcosinate useful herein can also preferably be prepared from the ester(preferably the methyl ester) of oleic acid and a sarcosine salt(preferably the sodium salt) under anhydrous reaction conditions in thepresence of a base catalyst with a basicity equal to or greater thanalkoxide catalyst (preferably sodium methoxide). For example, thereaction may be illustrated by the scheme: ##STR4##

This salt may optionally be neutralized to form the oleoyl sarcosinatein its acid form.

The preferred method for preparing oleoyl sarcosinate is conducted at atemperature from about 80° C. to about 200° C., especially from about120° C. to about 200° C. It is preferred to conduct the reaction withoutsolvent although alcohol solvents which have a boiling point of at least100° C. and are stable to the reaction conditions ie. glycerol is notacceptable) can be used. The reaction may proceed in about 85% yieldwith a molar ratio of methyl ester reactant to sarcosine salt reactantto basic catalyst of about 1:1:0.05-0.2.

Methyl ester mixtures derived from high oleic content natural oils(preferably having at least about 60%, more preferably at least about75%, and most preferably at least about 90% oleic content) areespecially preferred as starting materials. Examples include high-oleicsunflower and rapeseed/canola oil. In addition, a high-oleic methylester fraction derived from either palm kernel oil or tallow isacceptable. It is to be understood that such oils typically will containsome levels of impurities, including some fatty acid impurities that maybe convened to sarcosinate compounds by this synthesis method. Forexample, commodity canola/rapeseed oil may comprise a majority of oleicacid, and a mixture of fatty acid impurities such as palmitic, stearic,linoleic, linolenic and/or eicosenoic acid, some or all of which areconvened to the sarcosinate by this reaction method. If desired forformulation purposes, some or all of such impurity materials may beexcluded from the starting oil before preparing the oleoyl sarcosinateto be used in the present compositions.

Finally, sarcosine remaining in the reaction mixture can be converted toan amide by addition of maleic or acetic anhydride to the mixture,thereby minimizing the sarcosine content and any potential for formationof undesired nitrogen-containing impurities.

The synthesis of oleoyl sarcosinate may be carried out as follows toprepare the sodium oleoyl sarcosinate.

Synthesis of Oleoyl Amide of Sarcosine Sodium Salt - A 2 L, 3-neck,round bottom flask is fitted with thermometer, Dean-Stark trap withcondenser, mechanical stirring, and a gas inlet adapter through whichnitrogen is passed over the reaction mixture. The reaction vessel ischarged with sarcosine (43.3 g, 0.476 mol), sodium methoxide 25% inmethanol (97.7 g, 0.452 mol), and methanol (400 mL). The reaction isrefluxed 15 rain to neutralize the sarcosine and then methyl esterderived from Cargill regular high-oleyl sunflower oil (148.25 g, 0.5mol) is added. After the methanol is removed with the Dean-Stark trap,reaction mixture is heated to 170° C. for 1 hr to drive off any water.The reaction is initiated by the addition of sodium methoxide 25% inmethanol (15.4 g, 0.0714 tool). Reaction is kept at 170° C. for 2.5 hrduring which methanol is collected in the Dean-Stark trap. The reactionis allowed to cool slightly and then methanol ( 200 g) is added. Maleicanhydride (9.43 g, 0.095 mol) is added to the methanol solution and thereaction is stirred at 60° C. for 0.5 hr. Then most of the methanol isremoved by rotary evaporation and acetone (2 L) is added to precipitatethe product. The product is collected by suction filtration and allowedto air dry to give an off-white solid. Analysis of the reaction mixtureby GC indicates the majority of the product is oleoyl sarcosinate, withminor amounts of the following impurities: sarcosine, oleic acid, andthe sarcosinates derived from palmitic acid, stearic acid, and linoleicacid.

Polymeric Dispersing Agents Polymeric dispersing agents canadvantageously be utilized at levels from about 0.05% to about 15%,preferably from about 0.1% to about 10%, more preferably from about 0.1%to about 7%, by weight, in the compositions herein. Suitable polymericdispersing agents include polymeric polycarboxylates and polyethyleneglycols, although others known in the art can also be used.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000. A preferred copolymer hasan average molecular weight of about 2,000 to 15,000, more preferablyabout 6,000 to about 13,000, and most preferably about 7,000 to about12,000. Other preferred copolymers have an average molecular weight fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:2, more preferably from about 10:1 to1:1, and most preferably about 2.5:1 to 1:1. Water-soluble salts of suchacrylic acid/maleic acid copolymers can include, for example, the alkalimetal, ammonium and substituted ammonium salts. Soluble acrylate/maleatecopolymers of this type are known materials which are described inEuropean Patent Application No. 66915, published Dec. 15, 1982, as wellas in EP 193,360, published Sep. 3, 1986, which also describes suchpolymers comprising hydroxypropylacrylate. Still other useful dispersingagents include the maleic/acrylic/vinyl alcohol terpolymers. Suchmaterials are also disclosed in EP 193,360, including, for example, the45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Other preferred dispersant polymers are low molecular weight modifiedpolyacrylate copolymers. Such copolymers contain as monomer units: a)from about 90% to about 10%, preferably from about 80% to about 20% byweight acrylic acid or its salts and b) from about 10% to about 90%,preferably from about 20% to about 80% by weight of a substitutedacrylic monomer or its salt and have the general formula:--[(C(R²)C(R¹)(C(O)OR³)]-- wherein the incomplete valencies inside thesquare braces are hydrogen and at least one of the substituents R¹, R²or R³, preferably R¹ or R², is a 1 to 4 carbon alkyl or hydroxyalkylgroup, R¹ or R² can be a hydrogen and R³ can be a hydrogen or alkalimetal salt. Most preferred is a substituted acrylic monomer wherein R¹is methyl, R² is hydrogen and R³ is sodium.

The low molecular weight polyacrylate dispersant polymer preferably hasa molecular weight of less than about 15,000, preferably from about 500to about 10,000, most preferably from about 1,000 to about 5,000. Themost preferred polyacrylate copolymer for use herein has a molecularweight of 3500 and is the fully neutralized form of the polymercomprising about 70% by weight acrylic acid and about 30% by weightmethacrylic acid.

Other suitable modified polyacrylate copolymers include the lowmolecular weight copolymers of unsaturated aliphatic carboxylic acidsdisclosed in U.S. Pat. Nos. 4,530,766, and 5,084,535, both incorporatedherein by reference.

Agglomerated forms of the present invention may employ aqueous solutionsof polymer dispersants as liquid binders for making the agglomerate(particularly when the composition consists of a mixture of sodiumcitrate and sodium carbonate). Especially preferred are polyacrylateswith an average molecular weight of from about 1,000 to about 10,000,and acrylate/maleate or acrylate/fumarate copolymers with an averagemolecular weight of from about 2,000 to about 80,000 and a ratio ofacrylate to maleate or fumarate segments of from about 30:1 to about1:2. Examples of such copolymers based on a mixture of unsaturated mono-and dicarboxylate monomers are disclosed in European Patent ApplicationNo. 66,915, published Dec. 15, 1982, incorporated herein by reference.

Other dispersant polymers useful herein include the polyethylene glycolsand polypropylene glycols having a molecular weight of from about 950 toabout 30,000 which can be obtained from the Dow Chemical Company ofMidland, Mich. Such compounds for example, having a melting point withinthe range of from about 30° to about 100° C. can be obtained atmolecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000.Such compounds are formed by the polymerization of ethylene glycol orpropylene glycol with the requisite number of moles of ethylene orpropylene oxide to provide the desired molecular weight and meltingpoint of the respective polyethylene glycol and polypropylene glycol.The polyethylene, polypropylene and mixed glycols are referred to usingthe formula HO(CH₂ CH₂ O)_(m) (CH₂ CH(CH₃)O)_(n) (CH(CH₃)CH₂ O)_(o) Hwherein m, n, and o are integers satisfying the molecular weight andtemperature requirements given above.

Yet other dispersant polymers useful herein include the cellulosesulfate esters such as cellulose acetate sulfate, cellulose sulfate,hydroxyethyl cellulose sulfate, methylcellulose sulfate, andhydroxypropylcellulose sulfate. Sodium cellulose sulfate is the mostpreferred polymer of this group.

Other suitable dispersant polymers are the carboxylated polysaccharides,particularly starches, celluloses and alginates, described in U.S. Pat.No. 3,723,322, Diehl, issued Mar. 27, 1973; the dextrin esters ofpolycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson,issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters,oxidized starches, dextrins and starch hydrolysates described in U.S.Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylatedstarches described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21,1971; and the dextrin starches described in U.S. Pat. No. 4,141,841,McDanald, issued Feb. 27, 1979; all incorporated herein by reference.Preferred cellulose-derived dispersant polymers are the carboxymethylcelluloses.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. In compositionscontaining detergent builders, it is believed, though it is not intendedto be limited by theory, that polymeric dispersing agents enhanceoverall detergent builder performance, especially zeolite and/orsilicate builders, when used in combination with other builders(including lower molecular weight polycarboxylates) by crystal growthinhibition, particulate soil release peptization, and anti-redeposition.Dispersing agents such as polyaspartate preferably have a molecularweight (avg.) of about 10,000.

Detersive Surfactants - Surfactants useful herein typically at levels atleast about 1%, preferably from about 1% to about 55%, by weight,include the conventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") andprimary, branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), theC₁₀ -C₁₈ secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x)(CHOSO₃ ⁻ M⁺) CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and(y+1) are integers of at least about 7, preferably at least about 9, andM is a water-solubilizing cation, especially sodium, unsaturatedsulfates such as oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates("AE_(x) S"; especially x up to about 7 EO ethoxy sulfates), C₁₀ -C₁₈alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates),the C₁₀₋₁₈ glycerol ethers, the C₁₀ -C₁₈ alkyl polyglycosides and theircorresponding sulfated polyglycosides, and C₁₂ -C₁₈ alpha-sulfonatedfatty acid esters. If desired, the conventional nonionic and amphotericsurfactants such as the C₁₂ -C₁₈ alkyl ethoxylates ("AE") including theso-called narrow peaked alkyl ethoxylates and C₆ -C₁₂ alkyl phenolalkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂ -C₁₈betaines and sulfobetaines ("sultaines"), C₁₀ -C₁₈ amine oxides, and thelike, can also be included in the overall compositions. The C₁₀ -C₁₈N-alkyl polyhydroxy fatty acid amides can also be used. Typical examplesinclude the C₁₂ -C₁₈ N-methylglucamides. See WO 9,206,154. Othersugar-derived surfactants include the N-alkoxy polyhydroxy fatty acidamides, such as C₁₀ -C₁₈ N-(3-methoxypropyl) glucamide. The N-propylthrough N-hexyl C₁₂ -C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps may also be used. If high sudsing is desired,the branched-chain C₁₀ -C₁₆ soaps may be used. Mixtures of anionic andnonionic surfactants are especially useful. Other conventional usefulsurfactants are listed in standard texts.

Builders - Detergent builders can optionally be included in thecompositions herein to assist in controlling mineral hardness andcleaning. Inorganic as well as organic builders can be used. Buildersare typically used in fabric laundering compositions to assist in theremoval of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder. Liquidformulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric metaphosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 isthe trademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂ SiO₅ morphology form of layered silicate. It can be preparedby methods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x) O_(2x+1).yH₂ O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used herein. Various other layeredsilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as thealpha, beta and gamma forms. As noted above, the delta-Na₂ SiO₅ (NaSKS-6form) is most preferred for use herein. Other silicates may also beuseful such as for example magnesium silicate, which can serve as acrispening agent in granular formulations, as a stabilizing agent foroxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z/n [(AlO.sub.2).sub.z (SiO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are integers usually of at least 6, the molar ratio of zto y is in the range from 1.0 to 0, and x is an integer from 0 to about264, and M is a Group IA or IIA element, e.g., Na, K, Mg, Ca withvalence n.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et at, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids such as oleic acidand/or its salts, can also be incorporated into the compositions alone,or in combination with the aforesaid builders, especially citrate and/orthe succinate builders, to provide additional builder activity. Such useof fatty acids will generally result in a diminution of sudsing, whichshould be taken into account by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Enzymes - Enzymes can be included in the formulations herein for a widevariety of fabric laundering purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains, forexample, and for the prevention of refugee dye transfer, and for fabricrestoration. The enzymes to be incorporated include proteases, amylases,lipases, cellulases, and peroxidases, as well as mixtures thereof. Othertypes of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.However, their choice is governed by several factors such as pH-activityand/or stability optima, thermostability, stability versus activedetergents, builders and so on. In this respect bacterial or fungalenzymes are preferred, such as bacterial amylases and proteases, andfungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.001 mg to about 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from about 0.001% to about5%, preferably 0.01%-2% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE. The preparationof this enzyme and analogous enzymes is described in British PatentSpecification No. 1,243,784 of Novo. Proteolytic enzymes suitable forremoving protein-based stains that are commercially available includethose sold under the tradenames ALCALASE and SAVINASE by Novo IndustriesA/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (TheNetherlands). Other proteases include Protease A (see European PatentApplication 130,756, published Jan. 9, 1985) and Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985). Most preferred is what is called herein "Protease C", which is avariant of an alkaline serine protease from Bacillus, particularlyBacillus lentus, in which arginine replaced lysine at position 27,tyrosine replaced valine at position 104, serine replaced asparagine atposition 123, and alanine replaced threonine at position 274. Protease Cis described in EP 90915958:4; U.S. Pat. No. 5,185,250; and U.S. Pat.No. 5,204,015. Also preferred are protease which are described incopending application U.S. Ser. No. 08/136,797, entitledProtease-containing Cleaning Compositions and copending application U.S.Ser. No. 08/136,626, entitled Bleaching Compositions Comprising ProteaseEnzymes, which are incorporated herein by reference. Geneticallymodified variants, particularly of Protease C, are also included herein.

Amylases include, for example, α-amylases described in British PatentSpecification No. 1,296,839 (Novo), RAPIDASE, InternationalBio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulase usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, issued Mar. 6, 1984, which discloses fungal cellulaseproduced from Humicola insolens and Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk(Dolabella auricula Solander). suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) isespecially useful.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. See also lipasesin Japanese Patent Application 53,20487, laid open to public inspectionon Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P." Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EPO 341,947)is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S. It may be desired to use,in combination with these peroxidases, materials viewed as beingperoxidase accelerators such as phenolsulfonate and/or phenothiazine.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use indetergents can be stabilized by various techniques. Enzyme stabilizationtechniques are disclosed and exemplified in U.S. Pat. No. 3,600,319,issued Aug. 17, 1971 to Gedge, et al, and European Patent ApplicationPublication No. 0 199 405, Application No. 86200586.5, published Oct.29, 1986, Venegas. Enzyme stabilization systems are also described, forexample, in U.S. Pat. No. 3,519,570.

Enzyme Stabilizers - The enzymes employed herein are stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions which provide such ions to the enzymes.(Calcium ions are generally somewhat more effective than magnesium ionsand are preferred herein if only one type of cation is being used.)Additional stability can be provided by the presence of various otherart-disclosed stabilizers, especially borate species: see Severson, U.S.Pat. No. 4,537,706. Typical detergents, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 5 to about 15, and most preferably from about8 to about 12, millimoles of calcium ion per liter of finishedcomposition. This can vary somewhat, depending on the amount of enzymepresent and its response to the calcium or magnesium ions. The level ofcalcium or magnesium ions should be selected so that there is alwayssome minimum level available for the enzyme, after allowing forcomplexation with builders, fatty acids, etc., in the composition. Anywater-soluble calcium or magnesium salt can be used as the source ofcalcium or magnesium ions, including, but not limited to, calciumchloride, calcium sulfate, calcium malate, calcium maleate, calciumhydroxide, calcium formate, and calcium acetate, and the correspondingmagnesium salts. A small amount of calcium ion, generally from about0.05 to about 0.4 millimoles per liter, is often also present in thecomposition due to calcium in the enzyme slurry and formula water. Insolid detergent compositions the formulation may include a sufficientquantity of a water-soluble calcium ion source to provide such amountsin the laundry liquor. In the alternative, natural water hardness maysuffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance. Accordingly, as ageneral proposition the compositions herein will typically comprise fromabout 0.05% to about 2% by weight of a water-soluble source of calciumor magnesium ions, or both. The amount can vary, of course, with theamount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom about 0.25% to about 10%, preferably from about 0.5% to about 5%,more preferably from about 0.75% to about 3%, by weight of boric acid orother borate compound capable of forming boric acid in the composition(calculated on the basis of boric acid). Boric acid is preferred,although other compounds such as boric oxide, borax and other alkalimetal borates (e.g., sodium ortho-, meta- and pyroborate, and sodiumpentaborate) are suitable. Substituted boric acids (e.g., phenylboronicacid, butane boronic acid, and p-bromo phenylboronic acid) can also beused in place of boric acid. It is to be recognized that such materialsmay also be used in formulations as the sole stabilizer as well as beingused in combination with added calcium and/or magnesium ions.

Finally, it may be desired to add chlorine scavengers, especially toprotease-containing compositions, to protect the enzymes from chlorinetypically present in municipal water supplies. Such materials aredescribed, for example, in U.S. Pat. No. 4,810,413 to Pancheri et al.

Bleaching Compounds - Bleaching Agents and Bleach Activators - Thedetergent compositions herein may optionally contain bleaching agents orbleaching compositions containing a bleaching agent and one or morebleach activators. When present, bleaching agents will typically be atlevels of from about 1% to about 30%, more typically from about 5% toabout 20%, of the detergent composition, especially for fabriclaundering. If present, the amount of bleach activators will typicallybe from about 0.1% to about 60%, more typically from about 0.5% to about40% of the bleaching composition comprising the bleachingagent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning or other cleaningpurposes that are now known or become known. These include oxygenbleaches as well as other bleaching agents. Perborate bleaches, e.g.,sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from I to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR5##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR6## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl,or alkaryl group containing from 1 to about 12 carbon atoms. Highlypreferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. Nos. 5,246,621, 5,244,594; 5,194,416; 5,114,606; and European Pat.App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferredexamples of these catalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese withvarious complex ligands to enhance bleaching is also reported in thefollowing U.S. Pat. Nos.: 4,728,455; 5,284,944; 5,246,612; 5,256,779;5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Adjunct Ingredients - The compositions herein can optionally include oneor more other detergent adjunct materials or other materials forassisting or enhancing cleaning performance, treatment of the substrateto be cleaned, or to modify the aesthetics of the detergent composition(e.g., perfumes, colorants, dyes, etc.). The following are illustrativeexamples of such adjunct materials.

Polymeric Soil Release Agent - Any polymeric soil release agent known tothose skilled in the art can optionally be employed in the compositionsand processes of this invention. Polymeric soil release agents arecharacterized by having both hydrophilic segments, to hydrophilize thesurface of hydrophobic fibers, such as polyester and nylon, andhydrophobic segments, to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles and,thus, serve as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with the soil release agent tobe more easily cleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to about 30 oxypropylene units wherein said mixture containsa sufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least about 25% oxyethylene units and more preferably,especially for such components having about 20 to 30 oxypropylene units,at least about 50% oxyethylene units; or (b) one or more hydrophobecomponents comprising (i) C₃ oxyalkylene terephthalate segments,wherein, if said hydrophobe components also comprise oxyethyleneterephthalate, the ratio of oxyethylene terephthalate: C₃ oxyalkyleneterephthalate units is about 2:1 or lower, (ii) C₄ -C₆ alkylene or oxyC₄ -C₆ alkylene segments, or mixtures therein, (iii) poly (vinyl ester)segments, preferably polyvinyl acetate), having a degree ofpolymerization of at least 2, or (iv) C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether substituents, or mixtures therein, wherein saidsubstituents are present in the form of C₁ -C₄ alkyi ether or C₄hydroxyalkyl ether cellulose derivatives, or mixtures therein, and suchcellulose derivatives are amphiphilic, whereby they have a sufficientlevel of C₁ -C₄ alkyl ether and/or C₄ hydroxyalkyl ether units todeposit upon conventional polyester synthetic fiber surfaces and retaina sufficient level of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilicity, or acombination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used,preferably from 3 to about 150, more preferably from 6 to about 100.Suitable oxy C₄ -C₆ alkylene hydrophobe segments include, but are notlimited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_(n) OCH₂ CH₂₀ --, where M is sodium and n is an integer from 4-6,as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 toGosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from about 25,000 to about 55,000. See U.S. Pat. No.3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 toBasadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymerie soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoarolyl, end-cappedterephthalate esters.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises about one sulfoisophthaloyl unit, 5 terephthaloylunits, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of fromabout 1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)ethanesulfonate. Said soil release agent alsocomprises from about 0.5% to about 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof.

Chelating Agents - The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents - The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylates amines; liquid detergent compositions typically containabout 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein.

Brightener - Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.05% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide,azoles, 5- and 6-membered-ring heterocycles, and other miscellaneousagents. Examples of such brighteners are disclosed in "The Productionand Application of Fluorescent Brightening Agents", M. Zahradnik,Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and theaminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No. 3,646,015, issued Feb. 29, 1972to Hamilton. Anionic brighteners are preferred herein.

Suds Suppressors - Compounds for reducing or suppressing the formationof suds can be incorporated into the compositions of the presentinvention. Suds suppression can be of particular importance in theso-called "high concentration cleaning process" as described in U.S.Pat. Nos. 4,489,455 and 4,489,574 and in front-loading European-stylewashing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. U.S. Pat. No. 2,954,347, issuedSep. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids andsalts thereof used as suds suppressor typically have hydrocarbyl chainsof 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.Suitable salts include the alkali metal salts such as sodium, potassium,and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout -40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term "paraffin," as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing mount of a suds controlling agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight of said silicone sudssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. Nos. 4,978,471,Starch, issued Dec. 18, 1990, and 4,983,316, Starch, issued Jan. 8,1991, 5,288,431, Huber et al., issued Feb. 22, 1994, and U.S. Pat. Nos.4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 throughcolumn 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a "suds suppressing amount. By "suds suppressing amount" is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 5% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Fabric Softeners - Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for example, in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

Dye Transfer Inhibiting Agents - The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R-A_(x)-P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR7## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modern Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR8## wherein R₁ is selectedfrom anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selectedfrom N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-forming cation such as sodium orpotassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX, Tinopal-PLC, and/or Tinopal AMS-GX) providessignificantly better dye transfer inhibition in aqueous wash solutionsthan does either of these two detergent composition components when usedalone. Without being bound by theory, it is believed that suchbrighteners work this way because they have high affinity for fabrics inthe wash solution and therefore deposit relatively quick on thesefabrics. The extent to which brighteners deposit on fabrics in the washsolution can be defined by a parameter called the "exhaustioncoefficient". The exhaustion coefficient is in general as the ratio ofa) the brightener material deposited on fabric to b) the initialbrightener concentration in the wash liquor. Brighteners with relativelyhigh exhaustion coefficients are the most suitable for inhibiting dyetransfer in the context of the present invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds discussed above can optionally be used inthe present compositions to provide conventional fabric "brightness"benefits, rather than a true dye transfer inhibiting effect.

Other Ingredients - A wide variety of other ingredients useful indetergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀ -C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀ -C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.If desired, soluble magnesium salts such as MgCl₂, MgSO₄, and the like,can be added at levels of, typically, 0.1%-2%, to provide additionalsuds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5×the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be "protected" for use in detergents,including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarders. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

Granular detergents can be prepared, for example, by spray-drying (finalproduct density about 520 g/l) or agglomerating (final product densityabove about 600 g/l) the Base Granule. The remaining dry ingredients canthen be admixed in granular or powder form with the Base Granule, forexample in a rotary mixing drum, and the liquid ingredients (e.g.,nonionic surfactant and perfume) can be sprayed on.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

As used herein, all prescentages, parts, and ratios are by weight unlessotherwise stated. The following Examples illustrate the invention andfacilitate its understanding, they are not meant to limit the scope ofthe invention.

EXAMPLE I

A granular laundry detergent for washing machines is shown below.

    ______________________________________                                        A granular laundry detergent for washing                                      machines is shown below.                                                                            Wt. %                                                   ______________________________________                                        Sokalan CP5 (100% active as Na salt).sup.1                                                            3.52                                                  Dequest 2066 (100% as acid)                                                                           0.45                                                  Oleoyl sarcosinate      4.00                                                  Calcium formate         0.50                                                  Zeolite A               17.9                                                  Carboxy methyl cellulose                                                                              0.45                                                  Sodium Carbonate        9.4                                                   Citric acid             3.5                                                   Layered silicate SKS-6  12.9                                                  C.sub.18 sulfate        2.8                                                   C.sub.14-16 sulfate     2.0                                                   C.sub.12-15 alkyl ethoxy (3.0) sulfate                                                                1.0                                                   C.sub.12-16 amine oxide 10.0                                                  Branched fatty acid     2.0                                                   Neodol C.sub.18 E.sub.9 2.5                                                   Starch                  1.0                                                   Stearyl alcohol         0.15                                                  Sodium percarbonate (coated)                                                                          15.0                                                  Tetraacetylenediamine (TAED)                                                                          4.0                                                   Zinc phthalocyanin      0.02                                                  Water and other         balance                                               ______________________________________                                         .sup.1 Sokalan is sodium polyacrylate/maleate from Hoechst               

EXAMPLE II

Granular agglomerate formulations are as follows.

    ______________________________________                                                              Active Parts                                            Ingredient              A      B                                              ______________________________________                                        Linear alkyl sulfate     --    6.17                                           Alkyl ethoxy (avg 0.6) sulfate                                                                        10.1   5.03                                           Neodol 23-9             0.45   0.69                                           Neodol 23-3             0.45   --                                             Cn N-cocoyl N-methyl glucamide                                                                        0.89   --                                             Oleoyl sarcosinate      5.7    5.7                                            Polyacrylate            2.97   2.97                                           Poylethyleneglycol (MW > 1.000)                                                                       1.20   1.20                                           Sulfate (Table)         9.20   9.20                                           Sulfate (filler)        7.40   7.40                                           Zeolite                 24.3   24.3                                           Sodium carbonate        27.2   27.2                                           Diethylene triamine penta acetic acid                                                                 0.5    0.5                                            water and minors        balance                                               ______________________________________                                    

What is claimed is:
 1. A detergent composition comprising(a) at least0.1% of oleoyl sarconsinate of the formula: ##STR9## wherein M ishydrogen or a cationic moiety; and (b) from about 0.05% to about 15% ofa polymeric dispersing agent selected from the group consisting ofpolycarboxylates, polyethylene glycol polymers, polyaspartates andmixtures thereof.
 2. A detergent composition according to claim 1wherein said polymeric dispersing agent selected from the groupconsisting of polymeric polycarboxylates derived from acrylic acid,acrylic/maleic acid and mixtures thereof.
 3. A detergent compositionaccording to claim 2 comprising from about 1% to about 7% of saiddispersing agent and wherein said dispersing agent comprises polymerizedacrlyic acid or a soluble salt thereof and has an average molecularweight of from about 2,000 to about 10,000.
 4. A detergent compositionaccording to claim 1 wherein M is selected from hydrogen or alkali metalsalts.
 5. A detergent composition according to claim 4 wherein saidalkali metal salts is selected from sodium or potassium.
 6. A detergentcomposition according to claim 1 further comprising at least 0.5% of adetersive surfactant, other than said oleoyl sarcosinate surfactant,selected from anionic and nonionic detersive surfactants.
 7. A detergentcomposition according to claim 6 wherein said detersive surfactantcomprises alkyl sulfate, alkyl ethoxylated sulfates, alkyl estersulfonate, alkyl benzene sulfonates, alkyl ethoxylates, alkylpolyglycosides, alkyl phenol ethoxylates, paraffin sulfaontes,polyhydroxy fatty acid amides, and mixtures thereof.
 8. A detergentcomposition according to claim 7 comprising from about 1% to about 55%by weight of the composition of said detergent surfactant.
 9. Adetergent composition according to claim 1 further comprising at leastabout 1% detergent builder.
 10. A detergent composition according toclaim 9 wherein said builder is selected from the group consisting ofzeolite, silicate, carbonate, citrate and mixtures thereof.
 11. A methodfor cleaning substrates in aqueous solution with a detergent compositioncomprising detersive surfactant and a polymeric dispersing agent,wherein the improvement comprises including in said detergentcomposition at least about 0.1% by weight of the composition of a oleoylsarcosinate surfactant of the formula ##STR10## wherein M is a hydrogenor cationic moiety and wherein said dispersing agent is selected fromthe group consisting of polycarboxylates, polyethylene glycol polymers,polyaspartates and mixtures thereof.